O-carbamoyl-substituted acylchloride oxime



United States Patent 6 Claims. ((51.260-566) The present inventionrelates to and has as its objects new and useful fungicidal carbamicacid esters of the general formula in which R and R stand for optionallysubstituted aliphatic, cycloaliphatic, araliphatic or aromatic radicals,whilst R means hydrogen or an alkyl radical, and processes for theirpreparation.

As substituents of the above radicals R and R there may be consideredespecially halogen atoms, alkoxy, alkylmercapto, amino, alkyl, ordialkyl amino or nitro radicals.

R is a radical of the group consisting of lower alkyl radicalscontaining up to 4 carbon atoms, chloro-substituted lower alkyl radicalscontaining up to 4 carbon atoms, phenyl and substituted phenyl, thesubstituents of said substituted phenyl being up to 2 in number and ofthe group consisting of chloro, nitro and methoxy, R is a radical of thegroup consisting of lower alkyl radicals containing up to 4 carbon atomsand phenyl and substituted phenyl, the substituents of said substitutedphenyl being up to 2 in number and of the group consisting of loweralkyl, chloro, nitro and lower alkoxy and R is a radical of the groupconsisting of hydrogen and lower alkyl radicals containing up to 4carbon atoms.

In accordance with this invention the production of these carbamic acidesters having the above general for- 3,223,733 Patented Dec. 14, 1965materials for the process according to the invention can be obtained inthe manner known as such from the corresponding aldehydes andhydroxylamine and subsequent chlorination of the hydroxamic acidsformed.

As stated above the compounds obtainable according to the presentinvention possess an excellent fungicidal action. Hitherto only thioordithiocarbamic acid derivatives were known to exhibit these properties.This action covers a great number of phytopathogenic fungi, of whichwithout limiting the combatable fungi of plant diseases thereto, thefollowing shall be particularly mentioned:

Venturia inaequalis (Fusicladium dendritz'cum) Alternaria solaniPhytophthora infestans Plasmopara vitz'cola As an example for thesesurprising, technically valuable properties of the products according tothis invention there may serve the fungicidal action of the O-(N-methylcarbamoyl)-benzoyl chloride oxime (which could also be calledO-(N-methylcarbamoyl)hydroxyimino(alpha-chlorornethyl)benzene) havingthe formula when used against the fungi Plzytophthora infeszans, AI-lernaria solarzi and Plasmopara viticola.

(l) TESTING PHYTOPHTHORA INFESTANS Young potted tomato plants of theBonny Best variety with 4 to 5 foliage leaves are sprayed with aqueousemulsions o'r suspensions of the preparation at concentrations of theactive substance indicated below. 24 hours after spraying, the plantsare inoculated with zoo spores of the fungus Phytophthora infestans andsubsequently incubated at 100% relative atmospheric moisture and atemperature of 18 to 20 C. After 5 days, the infection of each pinnateleaf of the plants treated in the manner described above is determinedand expressed in of the infection of the untreated control plant theinfection degree of which is 100.

The results obtained are compiled in Table 1:

TABLE 1.F UN GICIDAL ACTION A GAINST PHYTOPHTHORA INFESTANS ON TOMATOESInfection degree in percent of the untreated control at a concentrationof Preparation preparation of- (|J=NOfi-NHCH, o 5 2s 34 Untreatedcontrol 100 mula may be carried out by methods known in principle, (2)TESTING A LTERNA RIA SOLANI e.g. either by reaction of the correspondingaliphatic, cycloaliphatic, araliphatic or aromatic hydroxamic acidchlorides with isocyanates or carbamic acid chlorides, or byphosgenation of the hydroxamic acid chlorides ON TOMATOES The test takesplace in principle in the same manner as that with Phytophthorainfestans, but the incubation mentioned and reaction of the resultingchloroformic or is carried out at a temperature of 23 to 25 C. and thebiscarbonic acid esters with primary or secondary amines. The hydroxamicacid chlorides required as starting evaluation of the test takes placealready 3 days after inoculation with spores of Alternaria solalzi.

The test results can be seen from Table 2:

' TABLE 2.-FUN G I'OI DAL ACTION AGAINST ALTERNARIA. SOLANI ON TOMATOESInfection degree in percent of Preparation the untreated control at aconcentration of preparation of 0.00625% t l=N-oo-r rnontm 39 Untreatedcontrol test 100 (3) TESTING PLASMOPARA VITICOLA ON VINES Young pottedvines of the Miiller-Thurgau variety with 5 to 7 developed leaves aresprayed in the manner indicated above. After the spray liquor has dried,inoculation with a zoo sporangium suspension of the fungus Plasmoparaviticola is carried out. The subsequent incubation takes place at to 23C. in air saturated with moisture. The evaluation of the test is carriedout after 6 days, the degree of infestation being determined in the samemanner as described under 1.

Table 3 gives a summary of the results obtained:

TABLE 3.FUNGICIDAL ACTION AGAINST PLASMOPARA VITICOLA ON VINES Thecompounds according to the invention are distinguished by a remarkableplant tolerance. Young tomato plants are not damaged by spraying with0.3% solutions of O-(N-methylcarbamoyl)benzoyl chloride oxime.

Carbamic acid esters, obtainable according to the process of theinvention as fungicides, can be used in the presence of suitablesolvents and emulsifiers in the form of aqueous emulsions. It is,however, also possible to mix the inventive agents together withsuitable auxiliary suspending agents and inert carriers, such as kaolin,bentonite or similar substances, and to employ them as aqueoussuspensions. Finally, the reparations may also be applied to the plantsto be protected in the form of dusting agents after mixing andoptionally grinding with suitable solid carrier materials. The combineduse of the compounds according to the invention with other fungicidesand/ or insecticides is possible.

The following examples are given for the purpose of illustrating theprocess claimed:

Example 1 A solution of 46.7 g. (0.3 mol) of benzoyl chloride oxime (C HC(Cl)=NOH) in 18.8 g. (0.33 mol) of methyl isocyanate (CH N=CO) istreated with 3 drops of triethylamine. After standing for 24 hours, theO-(N- methylcarbamoyl)benzoyl chloride oxime thus produced crystallizesout. After recrystallization from ligroin the compound melts at 83 to 84C.

Example 2 10.9 g. (0.07 mol) of benzoyl chloride oxirne are suspended in10 cc. of anhydrous benzene and this suspension is treated with 8.35 g.(0.07 mol) of phenylisocyanate and 3 drops of triethylamine. Afterstanding of the mixture for 24 hours, the benzene is distilled off andthe residue is recrystallized from ligroin. The O-(N-phenylcarbamoyl)benzoyl chloride examine thus produced melts at 136to 137 C.

In an analogous manner the following carb'amic acid esters having theformulae specified thereafter can be prepared:

0 (N 3 methylphenylcarbamoyl)benzoyl chloride MP. 87 to 89 C.

O (N 2 chlorophenylcarbamoyl)benzoyl chloride oxime M.P. to 85.5 C.

O (N 3 chlorophenylcarbamoyl)benzoyl chloride oxime MP. 107 to 108 C.

O (N 4 chlorophenylcarbamoyl)benzoyl chloride oxime MP. 141 to 142 C.

O-(N 3,4 dichlorophenylcarbamoyl)benzoyl chloride MP. to 151 C.

O-(N-4-nitrophenylcarbamoyl)benzoyl chloride oxime MP. 153 to 154 C.

O-(N-benzylcarbamoyl)benzoyl chloride oxime Example 31 23.3 grams (0.15mol) of benzoyl chloride oxime and the mixture is kept for 24 hours atroom temperature,v

Whereafter the crystallized pyridine hydrochloride is separated byfiltration. The benzene solution is washed with diluted hydrochloricacid, diluted sodium carbonate solution and finally with Water. Thesolution then is dried over sodium sulfate and the benzene is distilledoff in I vacuum. The residue crystallizes and may be recrystallized fromether. The O-(N,N-dimethylcarbamoyl)benzoyl chloride oxime thus producedhas a melting point of 6062 C.

the compounds represented by the following formulae 30 In an analogousmanner there may also be obtained 8 We claim: 1. AnO-carbamoyl-substituted acylchloride oxime having the formula RC=N-'OCNin which R is a radical of the group consisting of lower alkyl radicalscontaining up to 4 carbon atoms, chlorosubstituted lower alkyl radicalscontaining up to 4 carbon atoms, phenyl and substituted phenyl, thesubstituents of said substituted phenyl being up to 2 in number and ofthe group consisting of :chloro, nitro and methoxy, R is a radical ofthe group consisting of lower alkyl radicals containing up to 4 carbonatoms and phenyl and substituted phenyl, the substituents of saidsubstituted phenyl being up to 2 in number and of the group consistingof lower alkyl, chloro, nitro and lower alkoxy and R is a radical of thegroup consisting of hydro-gen and lower alkyl radioals containing up to4 carbon atoms.

2. The compound of the following formula 3. The compound of thefollowing formula 4. The compound of the following formula 5. Thecompound of the following formula 6. The compound of the followingformula References Cited by the Examiner Bellaveta: Gazz., chim. I-tal.,vol. 69, pp. 583-594 (1939).

Grammaticakis: Comptes rend, vol. 223, pp. 741-3 (1946).

Mangin-i: Gazz. chim. Ital., vol. 66, pp. 337-343 (1936).

CHARLES B. PARKER, Primary Examiner.

1. AN O-CARBAMOYL-SUBSTITUTED ACYLCHLORIDE OXIME HAVING THE FORMULA